New vat dyestuff



Patented Sept. 24, 1929- UNITED STATES 1,729,006 PATENT. OFFICE PAUL NAWIASKY AND EMIL "trauma, or LUDWIGSHAFEN-ON-THE-RHINE, GERMANY,

.assrenons 'ro GENERAL ANILINE wonxs, me, on NEW YORK, N. Y., A CORPORA- TION OF DELAWARE New -VAT DYESTUFF No Drawing. Application filed June 18, 1927, Serial No. 199,863; and in Germany June 22, 1926.

i speaking do not possess very good properties as regards fastness and especially fastness to light, unless the alkyl groups have only .a short chain of carbon atoms. a

We have now found that long-chain de- 19 rivatives also possess excellent properties as regards fastness provided they contain a short chain alkyl group containing not more than 4 carbon atoms in the chain to which a further hydrocarbon radicle is linked by means of an oxygen or a sulfur atom in sulfid form. The new dyestuits may be produced according to this invention, for example, by bringing the hydroxy-derivatives of dibenzanthrones or iso-dibenzanthrones hereinafter referred to collectively for the sake of brevity as dibenzanthrones into re action with arylsultonic-acid esters of alkyl-,

arylor aralkyl ethers of dior trivalent alcohols, or thioalcohols. The derivatives of ethylene glycol are particularly suitable, but those for example of propylene or butylene or other glycols or of glycerol or other polyvale'nt alcohols or thioalcohols may also be employed. In addition to their excellent fa'stness to light, the resulting dyestuffs are distinguished by a remarkably high solubility in organic solvents, such as has hitherto been scarcely known in the case of such high-molecular products. This ready solubility renders the new dyestuffs excellently suitable for example for the production of colored lacquers. The new prodticts obtained by the condensation of hydroxyderivatives of the ketones of theperylene series with toluene 'sulfonic acid esters of inonoalkyl others of ethyleneglycol have been found particularly useful.

The following examples will further illustrate how the said invention may be carried into practical effect but the invention is notlimited to these examples. The parts are by Weight.

10 parts of the reduced oxidation. obtained from dibcnzanthronc according to Example :-3 of the specification of Letters Patent No. 1.093.427 are hrau-d to boiling for 3 hours with 10 parts of g:lycol-mono-lucthyl-elhertoluenes ulfonate and 10 parts of sodium carbonate in 150 parts of triehlorbenzene.

'Another 5 parts of the ester and 5 parts of sodium carbonate are then added, and boiling is continued for another 3 hours under a reflux condenser. The whole is then allowed to cool slightly and the reaction mixture is subjected to steam distillation. The residue -1s purified by dissolving it in hot trichlorbe illustrated by the following equation: 7

CH:.O.CH: NazC 01-1-2 (I:

- Hz.O.SOz.CeHCH:

A similar dyestutt is obtained with ,glycoL mom r-cthyl-cther-tr:lucne-sulfonate.

E sample 2.

boiled for 3 hours under a reflux condenser 5 with 1O parts of glycol-mono-n-butyl-ethertoluene-sulfonate and parts of sodium carbonate in 150 parts of trichlorbenzene, after which another 10 parts of the said ester and 10 parts of sodium carbonate are added, and the heating is continued for 3 hours longer, under a reflux condenser, at boiling temperature. The further treatment is 'carried out in the manner described in Example 1. g

The reaction may be'illustrated'by the following equation;

CHaOCtHa NmCUri-Z The new dyestufi, is 'a dark powder of metallic lustre, which dissolves with comparative ease in benzene, and other organic solvents of low boiling point. A cellulose nitrate lacquer stained with the dyestnfi ,furmshes een coatings of a fastnesshithelfto unattainable with other green dyestuffs for cellulose nitrate lacquers.

Ii the glycol-butyl-ethertoluenesulfonate used for the'alkylating treatment contains also be obtained from ethylene bromide and dihydroxydibenzanthrone. In this case, thenew dyestufi' -.can be separated from the sparingly solubleblue dyestufi', for example 'by boiling with monochlorbenz'en'e or butyl acetate. V s

What we claim is:

11 As new articles of manufacture, ethers of hydroxy-derivatives of dibenzanthrones. in which the hydroxyl groups are etherified with ashort chain alkyl group containing at the most 4 carbon atoms in a further hydrocarbon radicl e is linked by means of an atom selected fromthe group consisting of oxygen and sulfur in sulfidform. V 2. As new articles of manufacture, ethers of dihydroxy-dibenzanthrone in which thehydroxyl groups are etherified with a, short chain alkyl group containing at the most 4 carbon atoms in" the chain to which a further hydrocarbon radicleis linked by means of an atom'selected from the group consisting of oxygen .and sulfur in sulfid form. T

3. As new article of manufacture anether of.dihydroxy-dibenzanthrone in which the hydrogen atoms of the liydrortyl roups are replaced by the grou H O H which ,product forms a dark powder of-metallic. lustre, is -..soluble in organic solvents of low boiling point and dissolves to a green solution in cellulose nitrate lacquers. 4. The process of producin new; vat dyestufi's which consists in etheri g hydroxyderivatives of dibenzanthrones with ashort chain alkyl rou containing at the most 4 carbon atomsin the chain to which a further hydrocarbon radicle is linked by means of an the chain to which U atom selected from-the group consisting of oxygen and sulfur in sulfid form.

sulfomc acid ester of an ether of a po' valent alcohol whichis at the most trivalent.

producing new vat 'dye- 6.- The processfo'fstufi's which consists in ether-ifying di- V hydrox-y-dibenzanthrone with an .aryl-sulfonic'acid' ester of an ether of a polyvalent alcohol which is at the most trivalent. 7. The process of producing new vat dyestufi's.- which consists in .etherifyin'g dihydroxy-dibenzanthrone with" an aryl-sulionic acid ester of a mono-alkyl ether of ethylene glycol. y;

In'testimony! whereof we have hereunto set our hands.

'PAUL NAWIASKY.

KRAUCH.

glycol-ditoluenesulfonate there is obtained,

by-product, 'a blue dyestufi, which can CERTIFICATE or CORRECTION.

Patent No. 1,729,006. Granted September 24, 1929, to

PAUL NA'WIASKY ET AL.

It is hereby certified that error appearsein the printed specification of the above numbered patent requiring correction as follows: Page 1, line 51, after the word "oxidation" insert the word "product"; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 15th day of October, A. D. 1929.

, M. J. Moore, (Seal) Acting Commissioner of Patents. 

